Inverse gas chromatography (IGC) is an attractive technique for polymer characterization due to possible simultaneous determination of various physicochemical properties of polymer systems merely from retention times of selected sorbates. The technique is especially advantageous to polymers that cannot be characterized by conventional methods. In this review, the utilization of the method for glass transition determination of homopolymers, copolymers and polymer blends is described. Advantages and drawbacks of the IGC method over traditionally used methods for glass transition temperature determination is discussed, along with the most important parameters that influence the precision and accuracy of the glass transition temperature (T(g)) measurements.